Mineral oil composition and additive therefor



Patented Sept. 19, 1950 1 I OIL COMPOSITION AND ADDITIVE Lawrence T.Eby, Roselle, N. J., assignor to Standard Oil Development Company, a,corporation, v

01 Delaware 1 No Drawing.

This invention relates to new chemical products and to improvedlubricating oils containing such products as additives.

Many types of chemical compounds have been proposed for use as detergentadditives for lubricating oils, for the purpose of dispersing sludge andmaintainin a clean engine condition when such oils are employed ascrankcase lubricants for internal combustion engines. Most of theadditives which have been found effective for such use contain metals,and while their sludge dispersing properties are satisfactory, there'isthe objection that a metal-containing deposit will be formed whichgradually becomes forced into the engine cylinder and tends to foul thespark plugs and produce other undesirable effects. It is accordingly anobject of the present invention to provide an additive which is aneffective detergent and at the same time contains no metal and isaccordingly entirely free from any tendency to form a deposit of thetype described.

The new class of additives which are described herein are non-metallicand have been found to possess the required degree of sludge dispersingand detergent properties, and these have been found to possess inaddition the property of inhibiting oxidation of the oil. They have alsobeen found to be valuable additives for extreme pressure lubricantscontaining chlorine compounds which tend to evolve hydrogen chlorideduring storage, the additive having the efl'ect of neutralizing suchcorrosive products without at the same time producing an objectionableprecipitate during periods of storage of a lubricant.

The new additives of the present invention, which are also new chemicalcompounds, are quaternary bases and salts formed by the alkylation ofdialkylaminomethyl phenol sulfides containing certain oil-solubilizingalkyl groups, as specified hereinafter. The new additives may be definedbroadly by the formulas in which R1, R2 and R3 are alkyl radicals with atotal of at last 9 carbon atoms, X is a hyppllcation Main, 1941,SerialNo.748,85 a, 11 Claims. (01. 252-415) 4 and preferably 8carbonatoms, 'andm, is a number from-1 to-" i'.-' The acid radicalswhich may be substituted for the hydroxyl groups of 'such quaternarybases maybe any acid radicals, whether inorganic or organic; ;The acidradicals which have been found to be particularly desirable for thepurpose of the present droxyl group or an inorganic or organic acidradical, R4 is hydrogen or an alkyliradical, R and R are alkyl radicals,each containing at least invention and which maybe readilyintroducedinto the compounds are those wh'ichare derived from the following acids:phosphoric, thiophosphoric, carbonic, thiocarbonic, sulfurous, sulfuric,mono-alkyl sulfuric, tetraisobute'nyl'sulfonic, thiocyanic,hydrochloric, nitric and boric.

In the preparation of the new compounds and additives of the presentinvention, alkylated phenols are first formed by reacting phenols witholeflns in the presence of an alkylating catalyst. From these themonosulfides and polysulfides may be formed by reaction with chloridesof sulfur. .The aminoalkylderivatives of such products may be formed byfirst preparing an alkylaminoalkyl-alkyl ether and then reacting thesame in the presence of an alcohol with the alkylated phenol sulfide.From the productsthus formed a quaternary ammonium base maybe derived bytreating with an alkylating agent,=such as a dialkyl sulfate or an alkylhalide, followed by reaction with a free base. Asan alternative method,the alkyl phenol sulfide may-first be converted into a chloralkylderivative by reaction 'with an aldehyde in the presence of hydrogenchloride, further reacting the product thus formed with a tertiaryamine, and finallyreacting the resulting chlorinated compound with abase. If it is desired to convert the base into a salt, the former maybe reacted with anacid or with an acid anhydride. Phosphoric orthiophosphoric acid salts may thus be formed by reaction with anoxideor'sulfide of phosphorus. Similarly, a thiocarbonate salt may beformedby reaction with carbon disulfide. The preparation of a number ofspecific examples .of the compounds of the present-invention isdescribed in detail below.

The quantity of the additives of the present invention which is mostadvantageously blended inthe mineral lubricating oil will depend uponrthe property of the additive which it is most desired'to exploit' Whenemployed for detergent and sludge dispersing purposes, the quantity mostsuitable will generally v'ary from Q1 't'o5%. For merely -inhibitingbearing corrosion andthe like the quantity most desirable will be, from0.05% 't0*2%. When the additive is to be femployed as 'a corrosioninhibitor in an extreme pressure lubricant composition, it is desir'ableto employ from 0.2% to 1%, particularly when "the lubricating" oilcontains abo t .0% of. a chlorinated hydrocarbon containing,approximately 32% chlorine.

Example 1.Di(di-n-octylmethylaminomethyl) tert-octyiphenol polysulfldehydroxide In a flask was placed 200 cc. of absolute ethyl alcohol, 120.5g. (0.5 mol) of di-noctylamine and 15 g. (0.5 mol CHzO) oftrioxymethylene. The mixture was stirred overnight to give a solution of0.5 mol of di-n-octylaminomethyl ethyl ether.

A solution of 1030 g. mols) of distilled tertoctylphenol and 1000 cc. ofchloroform was charged to a flask and stirred while 770 g. (7.5 mols) ofsulfur dichloride was added during 2 hours, keeping the temperaturebelow 30 C. The mixture was refluxed with stirring for 3 hours and thencooled, poured into water, extracted with ether, washed free ofhydrochloric acid, dried over sodium sulfate, and the solvent removed bydistillation, finishing at reduced pressure. The residue weighed 1506 g.and contained 15.61% sulfur (Parr Bomb), which corresponds to theformula on OK G CsHn C 51111 Half of the solution (0.25 mol) ofdi-n-octylhminomethyl ethyl etherdescribed abovewasadded to a solutionof 49.3 g. (0.102 mol) of the sulfurized phenol described above in 200cc. of absolute ethyl alcohol. The mixture was stirred and refluxedovernight. After cooling, 63 g. (0.5 mol) of dimethylsulfate was addedand the mixture stirred overnight. The volatile constituents wereremoved by vacuum distillation, finishing over a boiling water bath at 2mm. pressure. The residue weighing 173 g. was a brown viscous liquidwhich was found to contain 13.30% sulfur (Parr Bomb) and 1.95% nitrogen(Kjeldahl).

This di(di-n-octylmethylaminomethyl) -tertoctylphenol polysulfldedi(methyl sulfate) was dissolved in ether and stirred with aqueoussodium hydroxide'overnight. The ether layer was separated, washed withwater, dried over anhydrous potassium' carbonate, filtered, and theether removed by distillation. The residue was a brown liquid lessviscous than the methyl sulfate and contained 5.29% sulfur and 3.00%nitrogen. The product isdi(di-n-octylmethylaminomethyl)-tert-octylphenol polysulflde hydroxide.

Example 2.-Di n octylmethylaminomethyltert-octylphenol polysulfldehydroxide The same procedure as that used in Example 1 was used, exceptthat 98.5 g. (0.204 mol) of the alkylated phenol polysulflde was used.The din octylmethylaminomethyl tert octylphenol polysulflde was obtainedas a brown viscous liquid weighing 217.2 g. and containing 13.73% sulfurand 1.53% nitrogen. The free base was obtained by reacting such productwith sodium hydroxide solution as in Example 1, and was obtained as abrown viscous liquid not as viscous as the sulfate and containing 7.22%sulfur and 2.15% nitrogen.

Example 3.Thiophosphate of di(di-n-octylmethylaminomethyl)-tert-0ctylphenol polysulflde hydroxide 1030 g. (5 mols) of distilledtert-octylphenol and 1 l. of chloroform were placed in a flask equippedwith stirrer, dropping funnel, return condenser and thermometer. 386 g.(3.75 mols) of sulfur dichloride was dropped into the mixture whilestirring over a period of 6 hours, keeping the temperature below 30 C.The mixture was refluxed 6 hours, cooled and poured into water. Theorganic layer was removed, washed again with water and dried overanhydrous sodium sulfate. The mixture was filtered from the drying agentand stripped of solvent by vacuum distillation. The residue was areddish brown resin-like solid when cooled and weighed 1081.7 g. Theproduct contained 10.69% sulfur and thus corresponds approximately tothe formula OH OH CaHn CaHn 228.8 g. (0.5 mol) of the phenol sulfideproduct described above, 600 cc. of absolute ethyl alcohol, 241 g. (1mol) of di-n-octylamine and 30 g. (1 mol CHzO) of trioxymethylene werestirred together for one hour and then refluxed for one hour. Themixture was cooled to room temperature and 163.8 g. (1.3 mols) ofdimethyl sulfate was added with stirring to produce a solution ofdi(di-n-octylmethylamlnomethyl)-tert-octylphenol polysulflde di-(methylsulfate).

225 cc. of 25% of aqueous sodium hydroxide solution and 275 cc. of waterwere added to the alcohol solution of di(di-n-octylmethylaminomethyl)-tert-octylphenol polysulflde di- (methyl sulfate) described above. Themixture was stirred for 3 hours. The organic material was extracted with100 cc. of ether after dilution with 1 l. of water. The ether extractwas stirred with 100 cc. of 25% aqueous sodium hydroxide solution and100 cc. water for 3 hours. The organic layer was washed with three 500cc. portions of water and dried over anhydrous potassium carbonate.After filtering, the volatile materials were removed by vacuumdistillation, leaving 463.1 g. of brown viscousliquid residue whichcontained 4.86% sulfur and 2.61% nitrogen.

51.35 g. (0.05 mol) of di(di-n-octylmethylaminomethyl) -tert-octylphenolsulfide hydroxide, prepared as described in the preceding paragraph, and3.53 g. (0.0167 mol) of P285 were stirred together at room temperaturefor 20 hours. Hydrogen sulfide Was liberated. cc. of etherwas added andthe mixture stirred 24 hours. The ether was removed by distillationleaving a viscous dark reddish brown material containing 8.25% sulfur,2.37% nitrogen, and 1.88% phosphorus. The product is thus athiophosphate of di(di n octylmethylaminomethyl) tert octylphenolpolysulflde hydroxide.

Example 4.--Thz'ophosphate of di(di-n-octylmethylaminomethyl)-tert-octylphen ol polysulfide hydroxide liberated. 50 cc. of ether wasadded and the mix- .mixture was refluxed overnight.

ture stirred 24 hours The ether was removed by distillation, leaving aviscous dark reddish brown material containing 8.83% sulfur, 2.24%nitrogen and 1.97% phosphorus.

Example 5.-- Thiocarbonate' of I di(di-n-octylmethylaminomethyl)-tert-octylphenol polysulfide hydroxide 51.35 g. (0.05 mol) ofdi(di-n-octy1methylaminomethyl)-tert-octylphenol polysulfide hydroxide,prepared asdescribed in Example 3, and 25 cc. of carbon bisulfide werestirred together for 20 hours. There was no apparent liberation ofhydrogen sulfide, but a homogeneous solution formed with a rise intemperature of 3 C. The

solution was diluted with 50 cc. of ether and then stripped of volatileconstituents by vacuum distillation over a boiling water bath. Theresidue, weighing 51.2 g. was a reddish brown v scous liquid whichcontained 6.49% sulfur and 2.58% nitrogen. The product is thus athiocarbonate of di (di-n-octylmethylaminomethyl) -tert-octylphenolpolysulflde hydroxide.

Example 6.Dioctylmethylaminomethyl-tert-octylphenol polysulfide methylsulfate 1030 g. (5 mols) of distilled tert-octylphenol and 1 l. ofchloroform were placed in a flask equipped with stirrer, droppingfunnel, return condenser OH OH O aHn CaHn 228.5 g. (0.5 mol) of theproduct described above was dissolved in 600 cc. of absolute ethylalcohol and placed in a flask equipped with a dropping funnel. Asolution of 120.5 g. (0.5 mol) of di-n-octylamine and g. (0.5 mol CHzO)of trioxymethylene in 200 cc. of absolute ethyl alcohol was added slowlyfrom the dropping funnel. The After cooling, 126 g. (1 mol) of dimethylsulfate was added slowly with stirring. The mixture was stripped ofvolatile components by vacuum distillation and the residue was the brownvery viscous liquid weighing 509.9 g. and containing 11.36% sulfur and1.40% nitrogen. The product-was thusdi-noctylmethylaminomethyl-tert-octylphenol polysulfide methyl sulfate.

Example 7 .Di di-n-octylmethylwminomethyl tert-octylphewol polysulfidedi(methyl sulfate) Example 6 was repeated except-that 114.3 g. (0.25mol) of the polysulfide product was used. The product was a very viscousbrown liquid weighing 356.1 g. and containing 11.62% sulfur and 1.87%nitrogen. The product is di(di-n-octylmethylaminomethyl)-tert-octyphenol polysulfide di(methyl sulfate). I

Example 8.Di-n-octylmethylaminomethyl-tert- Octylphenol polysulfidehydroxide 374.2 g. of the productfrom Example 6'and 350 cc. of etherwere placed in a flask and stirred with 250 cc. of aqueous sodiumhydroxide solution. After stirring for 1.5 hours, the layers wereallowed to separate and the ether layer again stirred with 20% aqueoussodium hydroxide solution. The layers were separated and the ethersolution washed twice with water and then allowed to stand overnight toseparate any residual water in the organic layer. The volatileconstituents were removed from the organic layer by vacuum distillation.The residue was a brown viscous liquid weighing 290.5 g. and containing6.54% 81111111 and 1.88% nitrogen. This product wasdi-n-octylmethylaminomethyl-tert-octylphenol polysulfide hydroxide.

- Example 9.Di(di-n-octylmethylaminomethyl) tert-octylphenol polysulfldehydroxide 299.4 g. of the product from Example 7, and 300 cc. of etherwere placed in a flask and stirred with 200 cc. of 20% aqueous sodiumhydroxide solution. After stirring for 1 hours the layers were allowedto separate and the ether layer again stirred with 20% aqueous sodiumhydroxide solution. The layers were separated and the ether solutionwashed twice with water, dried over anhydrous potassium carbonate andstripped of vol v The atile constituents by vacuum distillation. residuewas a brown viscous liquid weighing. 198.8 g. and containing 4.99%sulfur and 2.70% nitrogen. This product wasdfldi-n-octylmethylaminomethyl)tert-octylphenol polysulfide hydroxide.

Til

Example 10.Di n butylmethylamlnomethyltert-butylphenol sulfide hydroxideA glass reaction flask was charged with 300.4 g. (2.0 'mols ofp-tert-butylphenol and 500 ml. of chloroform. The mixture was stirredand 103.0 g. (1.0 mols) of sulfur dichloride was added from a droppingfunnel over three hours while maintaining the temperature below 30 C.The solution was "heated under reflux for four hours, cooled, washedwith water, then with aqueous sodium bicarbonate solution and dried oversodium sulfate. The drying agent was removed by filtration and theorganic layer stripped ofsolventby distillation to a temperature of 115C. at

The residue was p-tert-butyl:

cohol, and 65.1 g. of di-n-butylamine was added to the flask and stirredfor one-half hour. The solution was heated under reflux for four hours.The solution was cooled and 126 g. (1 mol) of dimethyl sulfate was addedafter which the mixture was stirred for an additional two hours beforestripping to remove unreacted reagents and solvent. Stripping wascarried to C. at 2 mm. pressure to obtain 342.7 g. of residue, which isdin butylaminomethyl-tert butylphenol sulfide methyl sulfate. Thisproduct was not soluble in 1% concentration in either a 100 V. I. or 28V. I. mineral lubricating (S. A. E. 20) oil.

A glass flask was charged with 119.8 g. (0.205 mol) ofdi-n-butylmethylaminomethyl-tert-butylphenol sulfide methyl sulfate(prepared as described above), 200 ml. of benzene, and 100 nil. ofaqueous 25% sodium hydroxide solution. The mixture was stirred for 1.5hours and the aqueous layer then removed. Another 100 ml. of 25% sodiumhydroxide was added and the mixture stirred for 1.5 hours. The organiclayer was washed twice with distilled water. The second wash requiredcentrifuging to remove the water. The organic layer was Stripped to atemperature of 100 C. at 1 mm. The residue weighed 72.0 g. and was notcompletely soluble in the 100 V. I. S. A. E. 20 oil but the 1% solutionin the 28 V. I. oil was clear at room temperature. The residue was di nbutylmethylaminomethyl-tert-butylphenol sulfide hydroxide.

Example 11.-Carbon black dispersion tests A series of carbon blackdispersion tests were carried out, as described in U. S. Patent2,390,342, to measure the comparative efiectiveness of the additives ofthe present invention as agents for dispersing sludge in lubricatingoil. In these tests 6% by weight of activated carbon was added to theoil blend containing the additive and thoroughly dispersed in the oil bystirring with an "egg beater" type mixer for minutes while thetemperature of the oil was maintained at 250 F. 250 cc. of the blend wasthen placed in a 250 cc. graduated cylinder and allowed to settle for 24hours while the temperature was maintained at 200 F. If an additive isnot a dispersing agent, the carbon black settles rapidly at this pointleaving clear oil at the top in an hour or two. A very effectivedisperser will maintain the carbon black in suspension so that no changein the opaque slurry is apparent even after a 24- hour period. With allbut the most potent dispersing agents stratification occurs with a blacklayer at the botton (high concentration of carbon black) and a blueopaque layer at the top (reduced carbon black concentration). Cases ofthis type, known as "blue line separations, are only detectable inreflected light and the top oil contains smaller particles of dispersedcarbon black. Base oil A used in this test was a paraf- 8 lubricatingoil of S. A. E. 20 grade. The test was applied to the unblended base oilas well as to the blends. The test was conducted as follows: 500 cc. ofthe oil was placed in a glass oxidation tube (13 inches long and 2%inches in diameter) fitted at the bottom with a inch air inlet tubeperforated to facilitate air distribution. The oxidation tube was thenimmersed in a heatin bath so that the oil temperature was maintained at325 F. during the test. Two quarter sections of automotive bearings ofcopper-lead alloy of known weight having a totalarea of 25 sq. cm. wereattached to opposite sides of a. stainless steel rod which was thenimmersed in the test oil and rotated at 600 R. P. M., thus providingsufficient agitation of the sample during the test. Air was then blownthrough the oil at the rate of 2 cu. ft. per hour. At the end of each4-hour period the bearings were removed, washed with naphtha and weighedto determine the amount of loss by corrosion. The bearings were thenrepolished (to increase the severity of the test), reweighed,

' and then subjected to the test for additional finic oil of S. A. E. 20grade, while base oil B was a naphthenic oil of seconds viscositySaybolt at 210 F. The results of the test when applied to blendscontaining the products of Examples 1,

2, and 10 are shown in the following table, in

which the results are shown as the volume of oil below the line ofdemarcation and containing essentially all of the dispersed carbon blackafter the settling period.

Add Carbon Black 87 (top oil is clear).

Base Oil A 234 ("blue line" separation).

Base oil A+l% di (di-n-oetyl-methylaminomethyl)-tert-oetyl-phenolpolysulfide hydroxide (Example 1).

Base oil A+l% di-n-octyl-methylaminomethyl-tert-octyl-phenol polysulfldehydroxide (Example 2).

Base oil B Base oil B+1% di'n-butyl-methylaminomethyl-tert-butyl-phenolsulfide hydroxide (Example 10).

182 (blue line" separation).

115 (top 011 is deal). 134 ("blue line" separation).

Emample 12.Bearing corrosion tests Cc. Oil Containing Dispersed 4-hourperiods in like manner. The results are given in the following table ascorrosion life," which indicates the number of hours required for thehearings to lose 100 mg. in weight, determined by interpolation of thedata. obtained in the various periods.

Example 13.-Ea:treme pressure lubricant corrosion and stability testsThe ability of the additives of the present invention to preventcorrosion due to the extreme pressure agent of an extreme pressurelubricant was tested by incorporating 0.4% 01 each of several examplesof such additives in an extreme pressure lubricant consisting of of anacid and clay treated Coastal oil distillate having a viscosity of 70seconds Saybolt at 210 F. and 10% of an extreme pressure lubricantconsisting'of a sulfurized and chlorinated kerosene containing 6 to 7%sulfur and about 32% chlorine, and testing such blends in an S. A. E.Extreme Pressure Testing Machine. The machine was operated for 30seconds at 20 pounds load and then at 50 pounds load for 5 minutes. Thetest ring was placed in a desiccator containing a saturated solution ofsodium carbonate for 24 hours, washed with benzene and observed forevidence of corrosion. The amount of corrosion is given as thepercentage of the entire area which showed corrosion. a

Results are as follows:

Additive Per cent Blank Dioctylmethylaminomethyl-tert-octylpbenolpolysuiiidc methyl sulfate (Example 6) Di (di-n-octylmethylaminomethyl)iert-octylphenol polysulfide di-(mcthyl sulfate) (Example 7)Dioctylmethylaminomethyl-tert-octylphenol polysulfide hydroxide (Example8) Di (di-n-octylmethylaminomethyl) hydroxide (Example 9) preparing anextreme pressure agent described above containing 4 of an additive ofthe present invention, then storing such concentrate in a glass vesselin the presence of a steel strip for 24 hours at 150 F., after which thematerial was cooled and blended in 10% portions in a base stockconsisting of a Panhandle bright stock, which is a highly parafiinicoil, and observing the condition of the oil after 10 days storage atroom temperature. Blends prepared withdioctylmethylaminomethyl-tert-octylphenol polysulfide methyl sulfate andwith dioctylmethylaminomethyl-tert-octylphenol polysulfide hydroxide,the same being two of the additives tested for corrosion preventingability in this example, showed the additives to be completely solubleafter the storage period.

The products of the present invention may be employed not only inordinary hydrocarbon lubricating oils but also in the heavy duty type oflubricating oils which have been compounded with such detergent typeadditives as metal soaps, metal petroleum sulfonates, metal phenates,metal alcoholates, metal alkyl phenol sulfides, metal organo phosphates,thiophosphates, phosphites and thiophosphites, metal salicylates,

metal xanthates and thioxanthates, metal thiocarbamates, amines andamine derivatives, reaction products of metal phenates and sulfur, re-

phenyl stearate, zinc diisopropyl salicylate, 1,

aluminum naphthenate, calcium cetyl phosphate, barium di-tert-amylphenolsulfide, calcium petroleum sulfonate, zinc methyl cyclohexylthiophosphate, calcium dichlorostearate, etc. Other types of additives,such as phenols and phenol sulfides may also be employed.

The lubricating oil base stocks used in the compositions of thisinvention may be straight mineral lubricating oils or distillatesderived from parafiinic, naphthenic, asphaltic or mixed base crudes, or,if desired, various blended oils maybe employed as well as residuals,particularly those from which alphaltic constituents have been carefullremoved. The oils may be refined by conventional methods using acid,alkali and/or clay or other agents such as aluminum chloride, or theymay be extracted oils produced, for example, by solvent extraction withsolvents of the type of phenol, sulfur dioxide, furfural, di-

chlorodiethyl ether, nitrobenzene, crotonalde-- hyde, etc. Hydrogenatedoils or white oils may be employed as well as synthetic oil prepared,for example, by the polymerization of olefins or by the reaction ofoxides of carbon with hydrogen or by the hydrogenation of coal or itsproducts. In certain instances cracking coil tar fractions and coal taror shale oil distillates may also be used. Also, for specialapplications, animal, vegetable or fish oils or their hydrogenated orvoltolized products may be employed in admixture with mineral oils.

For the best results the base stock chosen should normally be that oilwhich without the new additive present gives the optimum performance inthe service contemplated. However,

1'0 since one advantage of the additives is that their use also makesfeasible the employment of less satisfactory mineral oils or other oils,no strict rule can be laid down for the choice of the base stock.Certain essentialsmust of course be observed. -The oil must possess theviscosity and volatility characteristics known to be required for theservice contemplated. The oil must be a satisfactory solvent for theadditive, although in some cases auxiliarysolvent agents may be used.The lubricating oils, however they may have been .produced, may varyconsiderably in viscosity and other properties depending upon thepatricular use for which they are desired. but they usually range fromabout 40, to 150 seconds Saybolt viscosity. at 210 F. ,For thelubricating of certain low and medium speed Diesel engines the generalpractice has often been to use a lubricating oil base stock preparedfrom naphthenic or aromatic crudes and having aSaybolt viscosity at 210F. of 45 to 90 seconds and a viscosity index of 0 to 50. However, incertain types of Diesel engine and other gasoline engine service, oilsof higher viscosity index are often preferred, for example, up to 75 to100, or even higher, viscosity index. 7

In addition to the materials to be added according to the presentinvention, other agents may also be used such as dyes, pour depressors,

heat thickened fatty oils, sulfurized fatty oils,

organo-metallic compounds, metallic .or other soaps, sludge dispersers,antioxidants, thickeners,

viscosityindex improvers, oiliness agents, resins, I

rubber, olefin polymers, voltolized fats, voltolized mineral oils,and/or voltalized waxes and colloidal solidssuch as graphite or zincoxide, etc. Solvents and assisting agents, such as esters, ketones,

referred to as. octadecyl alcohol (CmHa'rOH), heptadecyl-alcohol(C17H35OH), and the like, the

corresponding olefinic alcohols such as oleyl alcohol; cyclic alcoholssuch as naphthenic alco-- hols; and aryl substituted alkyl alcohols, forinstance, phenyl octyl alcohol, or octadecyl benzyl alcohol or mixturesof these various alcohols, which may be pure or substantially puresynthetic alcohols. One may also use mixed naturally occurring alcoholssuch as those found in wool fat (which is known to contain a substanetial percentage of alcohols having about 16 to 8 carbon atoms) and insperm oil (which contains a high percentage of cetyl alcohol); andalthough it is preferable to'isolate the alcohols from those materials,for some purposes, the wool fat, sperm oil or other natural productsrich in alcohols may be used per se. Products prepared synthetically bychemical processes may also be used, such as .alcohols prepared by theoxidation of petroleum hydrocarbons, e. g., paraffln wax, petrolatum,etc.

In addition to being employed in crankcase lubricants the additives ofthe present invention may also be used in extreme pressure lubricants,engine flushing oils, industrial oils, general machinery oils, processoils, rust preventive compositions and greases.

but is to be limited solely by the terms of the appended claims.

I claim:

l. A composition consisting essentially of a hydrocarbon base containing0.05 to of a compound of the formula OH on I }s-E I I wherein R and Rare alkyl radicals each containing at least 4 carbon atoms, 11. is anumber from 1 to 4, and wherein there is attached to the benzene nucleione to two radicals, not more than one such radical to a given benzenenucleus, of the formula R: i wherein R1, R2, and Rs are alkyl radicalscontaining an overall total of at least 9 carbon atoms and X is a memberof the group consisting of hydroxyl radicals and acid radicals derivedfrom water-soluble acids having an ionization constant at least as greatas 3.5 x

2. A mineral lubricating oil containing 0.05 to 5% of a compound of theformula wherein R and R' are alkyl radicals each containing. at least 4carbon atoms, 12. is a number from 1 to 4, and wherein there is attachedto the benzene nuclei one to two radicals, not more than onesuch radicalto a given benzene nucleus, of the formula wherein R1, R2, and R3 arealkyl radicals containing an overall total of at least 9 carbon atomsand X is a member of the group consisting oi hydroxyl radicals and acidradicals derived from water-soluble acids having an ionization constantat least as great as 3.5 x 10".

3. A mineral lubricating oil composition according to claim 2 in which Xof the formula is OH, and R and R are each CaHn.

4. A mineral lubricating oil composition according to claim 2 in which Xof the formula is OH, R1, R2, R, and R are each CaH17, and Rs is CH3.

5. A mineral lubricating oil composition according to claim 2 in which Xis a thiophosphate radical, R1, R2, R, and R are each CaHn, and R3 isCHa.

6. A mineral lubricating oil composition according to claim 2 in which Xis a thiocarbonate radical, R1, R21, R, and R are each CaHu, and R3 isCH3.

7. As a new compound a compound of the formula on OH I 3-$E I wherein Rand R are alkyl radicals each containing at least 4 carbon atoms, n is anumber from 1 to 4, and wherein there is attached to the benzene nucleione to two radicals, not more than one such radical to a given benzenenucleus, of the formula wherein R1, R2, and Rs are alkyl radicalscontaining an overall total of at least 9 carbon atoms. and X is amember of the group consisting of hydroxyl radicals and acid radicalsderived from water-soluble acids having an ionization constant at leastas great as 3.5 x 10-".

8. A compound according to claim 7 in which X of the formula is OH, andR and R are each CaHi'z.

9. A compound according to claim 7 in which X is OH, R1, R2, R and R areeach CeHn, and Ra is CH3.

10. A compound according to claim 7 in which X is a thiophosphateradical, R1, R2, R and R are each CaHvz, and R3 is CH3.

11. A compound according to claim 7 in which X is a thiocarbonateradical, R1, R11, R, and R are each CsHn, and R3 is CH3.

LAWRENCE T. EBY.

REFERENCES CITED The following references are of record in the flle ofthis patent:

UNITED STATES PATENTS Number Name Date 2,218,739 Bruson Oct. 22, 19402,260,967 Bruson Oct. 28, 1941 2,334,594 Zimmer et a1 Nov. 16, 19432,345,239 Cook et al Mar. 28, 1944 2,363,134 McCleary Nov. 21, 19442,416,265 Mac Mullen et al. Feb. 18, 1947 2,431,011 Zimmer et al Nov.18, 1947

1. A COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON BASE CONTAINING0.05 TO 5% OF A COMPOUND OF THE FORMULA